Wood preservatives based on inorganic copper compounds with alkanolamines as complexing agents are known (European Patent 89,958). Despite high copper contents, the activity of these agents against wood-destroying Basidiomycetes is insufficient in comparison with known copper- and chromate-containing salts having a comparable copper content.
It has now been found that wood preservatives based on copper compounds and alkanolamines, which contain a triazole compound and an emulsifier or which contain a phosphonium compound, have very good activity against wood-destroying Basidiomycetes. The present invention relates to mixtures which contain a triazole compound and an emulsifier, to mixtures which contain a phosphonium compound and to mixtures which contain a triazole compound, an emulsifier and a phosphonium compound.
In spite of the content of copper compounds in the wood preservative, on dilution with water the triazole compounds form a clear emulsion. The advantage of the novel agents is that triazole compounds which are insoluble in water are present in the novel agents in the the form of aqueous emulsions or clear aqueous concentrates. Clear aqueous liquids are formed on dilution with water.
Homogeneous concentrates can be obtained by adding small amounts of organic solvents to the wood preservative, for example alcohols (ethanol or isopropanol), glycols (ethylene glycol or propylene glycol), glycol ethers (ethylene glycol monomethyl ether or ethylene glycol monoethyl ether), glycol ether esters (butylglycol acetate), dimethylformamide or N-methyl-pyrrolidone. The solvents additionally act as solubilizers for the triazoles. With the additional use of arylcarboxylic acids, cycloalkylcarboxylic acids or aliphatic C5-C20-mono- or dicarboxylic acids or corresponding amine, alkali metal or copper salts, however, the use of solvents can be reduced to a minimum for obtaining homogeneous concentrates.
The copper compounds can be used as water-soluble or water-insoluble compounds, for example copper sulfate, copper acetate, copper hydroxide, copper oxide, copper borate, copper fluoride or basic copper carbonate.
An alkanolamine is, in particular, monoethanolamine; the use of other alkanolamines, for example isopropanolamine, 1,1- or 1,2-diaminoethanol, aminoethylethanolamine, diethanolamine, triethanolamine or methylethanolamine, is possible.
The amount of added alkanolamines is advantageously such that a pH of 7 or more, preferably from 8.5 to 10.5, is established in the dilute aqueous impregnating solution. The amount of amines should be sufficient for complexing the copper (1 g atom of copper requires about 4 mol equivalents of amine).
A triazole compound is, for example, 1-(2-(2,4-dichlorophenyl)-4-methyl-1,3-dioxolan-2-yl-methyl)-1H-1,2,4-triazole, 1-(2-(2,4-dichlorophenyl)-1,3-dioxolan-2-ylmethyl)-1H-1,2,4-triazole (azaconazole), 1-(2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-methyl)-1H-1,2,4-triazole, 1-(2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl)-1H-1,2,4-triazole (propiconazole), 1-(2-(2,4-dichlorophenyl)-4-phenyl-1,3-dioxolan-2-yl-methyl)-1H-1,2,4-triazole or xcex1-tert-butyl-a-(p-chlorophenylethyl)-H-1,2,4-triazole-1-ethanol (tebuconazole).
An emulsifier is, for example, an anionic, cationic or nonionic emulsifier or a mixture thereof. Nonionic emulsifiers are, for example, adducts of ethylene oxide (EO) or propylene oxide or mixtures thereof with organic hydroxy compounds, for example alkylphenols, fatty acids, fatty alcohols and mixtures thereof. Examples of suitable cationic emulsifiers are quaternary ammonium compounds and/or salts of fatty amines (for example dimethyl-(C12-C14)-alkylamines).
A quaternary ammonium compound is, for example, a compound of the general formula R1R2R3R4N+Zxe2x88x92, where R1 is alkyl of 8 to 20 carbon atoms, in particular alkyl of 12 to 20 carbon atoms or benzyl which is unsubstituted or substituted by C1-C20-alkyl or halogen, R2 is C1-C6-alkyl, C3-C9-alkoxyalkyl or polymeric ethylene oxide (EO) or propylene oxide (PO) where the number of EO or PO units n is from 2 to 50, R3 is C1-C6-alkyl, C3- or C4-alkoxy or polymeric ethylene oxide (EO) or propylene oxide (PO) where the number of EO or PO units n is from 2 to 50 and R4 is C1-C20-alkyl, or two of the radicals R1 to R4, together with the nitrogen atom, form a heterocyclic radical which contains 4 or 5 carbon atoms and one, two or three double bonds, the carbon atoms being unsubstituted or substituted by C1-C4-alkyl or halogen, and Z is an acid radical, eg. halide.
Particularly suitable phosphonium compounds are compounds of the formula
R13R2P+Yxe2x88x92
where R1 is alkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbon atoms or phenyl, R2 is alkyl of 8 to 18 carbon atoms and Y is an acid radical, in particular a halide anion.
R1 and R2 are preferably straight-chain.
The quaternary phosphonium compounds may be present individually or as mixtures in the novel concentrates. Examples of such phosphonium compounds are trimethyl-n-dodecylphosphonium chloride, triethyl-n-decylphosphonium bromide, tri-n-propyl-n-tetradecylphosphonium chloride, trimethylol-n-hexadecylphosphonium chloride, tri-n-butyl-n-tetradecylphosphonium chloride, tri-n-butyl-n-dodecylphosphonium bromide, tri-n-butyl-n-decylphosphonium chloride, tri-n-butyl-n-hexadecylphosphonium bromide, tri-n-hexyl-n-decylphosphonium chloride, triphenyl-n-dodecylphosphonium chloride, triphenyl-n-tetradecylphosphonium bromide and triphenyl-n-octadecylphosphonium chloride.
Aliphatic carboxylic acids can be added to improve the homogeneity of the concentrates. Examples of such acids are propionic acid, hexanoic acid, heptanoic acid, branched carboxylic acids, eg. 2-ethylenehexanoic acid or isooctanoic acid, neocarboxylic acids, aliphatic dicarboxylic acids, eg. sebacic acid, cycloalkylcarboxylic acids, eg. cyclohexanoic acid, and arylcarboxylic acids, eg. benzoic acid or 3- or 4-hydroxybenzoic acid.
When the abovementioned acids are used, it is advantageous in some cases to improve the penetration of the wood preservative in large scale industrial processes by adding complex-forming, polymeric nitrogen compounds, eg. polyethyleneimines.
Polyethyleneimines (PEI, polymin) are known and are formed by polymerization of 1,2-ethyleneimine. They contain the nitrogen in primary (terminal group), secondary or tertiary (branching) form. Polyethyleneimines where n is greater than 10 are suitable; very good results are obtained when PEI having a degree of polymerization n between 50 and 1,000 are used.
The wood preservatives may, if required, contain further compounds, for example compounds having a fungicidal anion, such as a boron compound (for example alkali metal borate, aminoborate, boric acid or boric ester) and fluorides (for example potassium fluoride and/or salts of fluoboric acid and/or fluophosphoric acid and/or difluophosphoric acid).
The action spectrum of the novel wood preservatives can, if required, be improved by adding further active ingredients. Examples of suitable compounds are N-organodiazeniumdioxy compounds, organotin compounds, in particular tributyltin (TBT) compounds and isothiazoline compounds of the following formula 
where R1 is hydrogen, an alkyl, alkenyl or alkynyl radical of 1 to 18 carbon atoms, cycloalkyl having a C3-C6-ring and not more than 12 carbon atoms or an aralkyl or aryl radical of not more than 19 carbon atoms and R2 and R3 independently of one another are hydrogen, halogen or C1-C4-alkyl, or R2 and R3 are part of an aromatic radical.
It is also possible to add further fungicides or insecticides, for example in emulsified form, such as N-tridecyl-2,6-dimethylmorpholine (tridemorph) and/or 4-(3-para-tert-butylphenyl)-2-methyl-propyl-2,6-cis-dimethylmorpholine (fenpropimorph) and/or chlorinated phenols tetrachloroisophthalodinitrile N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide N-dimethyl-Nxe2x80x2-phenyl-(N-fluoromethylthio)-sulfamide N,N-dimethyl-Nxe2x80x2-toluyl-(N-fluoromethylthio)-sulfamide methyl benzimidazole-2-carbamate 2-thiocyanomethylthiobenzothiazole 2-iodobenzanilide 1-(1xe2x80x2, 2xe2x80x2, 4xe2x80x2-triazol-1xe2x80x2-yl)-1-(4xe2x80x2-chlorophenoxy)-3,3-dimethylbutan-2-one 1-(1xe2x80x2, 2xe2x80x2, 4xe2x80x2-triazol-1xe2x80x2-yl)-1-(4xe2x80x2-chlorophenoxy)-3,3-dimethylbutan-2-ol hexachlorocyclohexane O,O-diethyldithiophosphorylmethyl-6-chlorobenzoxazolone 2-(1,3-thiazol-4-yl)-benzimidazole N-trichloromethylthio-3,6,7,8-tetrahydrophthalimide N-(1,1,2,2-tetrachloroethylthio)-3,6,7,8-tetrahydrophthalamide N-trichloromethylthiophthalimide 3-iodo-2-propylbutyl carbamate O,O-dimethyl S-(2-methylamino-2-oxoethyl) dithiophosphate O,O-dimethyl O-(3,5,6-trichloro-2-pyridyl) thiophosphate O,O-dimethyl S-(N-phthalimido)-methyl dithiophosphate O,O-diethyl O-(xcex1-cyanobenzylideneamino) thiophosphate 6,7,8,9,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,3,4-benzodioxothiepene 3-oxide (4-ethoxyphenyl)-(dimethyl)-3-(4-fluoro-3-phenoxyphenyl)-propyl silane 2-sec-butylphenyl N-methylcarbamate 2-propoxyphenyl N-methylcarbamate 1-naphthyl N-methylcarbamate norbornene dimethanohexachlorocyclosulfite 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)-urea synthetic pyrethroids, such as 3-phenoxybenzyl (+)-3-(2,2-dichlorovinyl-2,2-dimethyl)-cyclopropane-1-carboxylate xcex1-cyano-3,3-phenoxybenzyl 3-(2,2-dichlorovinyl-2,2-dimethyl)-cyclopropane-1-carboxylate 3-(2,2-dibromovinyl-2,2-dimethyl)-xcex1-cyano-m-phenoxybenzyl (1R,3R)-cyclopropanecarboxylate (deltamethrin) xcex1-cyano-3-phenoxybenzylisopropyl-2,4-chlorophenyl acetate.
In concentrated form, the water-dilutable wood preservatives generally contain the copper, for example, in an amount of from 1.0 to 15.0% by weight, calculated as metal.
Suitable concentrates consist of, for example,
from 2.50 to 45%, in particular 10 to 20%, of copper compounds,
from 5.00 to 50%, in particular 20 to 40%, of alkanolamine,
from 0.25 to 15%, in particular 1 to 10%, of triazole compounds,
from 2.50 to 40%, in particular 10 to 20%, of phosphonium compounds,
from 0.5 to 30%, in particular 5 to 15%, of an emulsifier,
from 0 to 40% of a compound having a fungicidal inorganic or organic anion,
from 0 to 40% of an organic solvent,
from 0 to 40% of an aliphatic mono- or dicarboxylic acid and/or cycloalkylcarboxylic acid and/or cycloarylcarboxylic acid and
from 0 to 15% of a complex-forming, polymeric nitrogen compound,
the sum being 100% by weight in each case, and, if required, minor amounts of other components, for example ammonia, corrosion inhibitors, complex-forming acids (eg. nitrilotriacetic acid or ethylenediaminetetraacetic acid where water of relatively high hardness is used) and, if required, water, the amount of which however can generally be kept small and which essentially serves handling purposes.
In addition to the wood preservatives (concentrates), the present invention also relates to the impregnating solutions of correspondingly lower individual concentration which can be prepared by diluting the concentrates with water. The application concentration corresponds to, for example, from 0.01 to 1.50% by weight of metal, eg. copper, in the aqueous impregnating solution, depending on the method of impregnation and the level of risk to which the wood to be impregnated is exposed.
Dissolving the copper salts, if necessary with heating, in the alkanolamines, with or without the addition of acid, water or solvents, and subsequent addition of the emulsifier, the triazole compounds and/or phosphonium compounds result in the formation of highly concentrated pastes, liquid concentrates or two-phase mixtures which, after dilution with water, can be used for impregnating wood. They give a clear liquid in water, even at a high concentration.
The impregnating solution can be used for preserving wood by manual methods, such as spraying, brushing on, immersion or trough impregnation, or by large-scale industrial processes, such as the pressure process, alternating pressure process or double vacuum process. Wood is understood both as solid wood and as woodworking materials, such as particle boards or plywood; here, the wood preservative may also be introduced in the glue mixing process.
The degree of fixing of the copper in the novel preservatives is high; it is more than 90% when large scale industrial methods are used.
The concentrates or solutions can be colored by water-soluble or water-emulsifiable dyes and/or pigment preparations.
Wax, paraffin and/or acrylate dispersions may be added to achieve a water-repellant effect or to improve the fixing.
The concentrates can, if required, also be incorporated in binder-containing water-dilutable systems (primers or transparent coats).
The Examples which follow illustrate the invention.
Determination of the limit of action against wood-destroying fungi
The method is used for determining the preventive action of wood preservatives against wood-destroying fungi.
Identical wooden blocks (5xc3x972.5xc3x971.5 cm) dried to a constant weight at 103xc2x0 C. are completely impregnated with stepwise amounts of the wood preservative to be tested and are dried, washed thoroughly with water (washing out the active ingredient mixture from the wood) and exposed to attack by cultures of wood-destroying fungi in glass dishes. The nutrient medium used for the fungi is malt agar (containing 4% of malt extract). The destruction of the wood caused by the fungal attack is measured by the weight loss of the wood specimens; a weight loss of 2% or more is evaluated as wood destruction.
A lower active ingredient concentration at which the wood just begins to be destroyed and an upper active ingredient concentration at which no wood destruction is detectable and hence complete wood preservation has been achieved are stated. It is always necessary to start from the upper active ingredient concentration for evaluating a wood preservative in practice.
The determination of the limit of the action against wood-destroying fungi (in kg of active ingredient or mixture of active ingredients per m3 of wood)
The result should be understood as follows. The lower the limit, the better the fungicidal action. 1 kg/m3 is thus better than 2 kg/m3.